Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function

Arne Scherrer, Federica Agostini, Daniel Sebastiani, E. K.U. Gross, Rodolphe Vuilleumier

Research output: Contribution to journalArticlepeer-review

57 Scopus citations

Abstract

The nuclear velocity perturbation theory (NVPT) for vibrational circular dichroism (VCD) is derived from the exact factorization of the electron-nuclear wave function. This new formalism offers an exact starting point to include correction terms to the Born-Oppenheimer (BO) form of the molecular wave function, similar to the complete-adiabatic approximation. The corrections depend on a small parameter that, in a classical treatment of the nuclei, is identified as the nuclear velocity. Apart from proposing a rigorous basis for the NVPT, we show that the rotational strengths, related to the intensity of the VCD signal, contain a new contribution beyond-BO that can be evaluated with the NVPT and that only arises when the exact factorization approach is employed. Numerical results are presented for chiral and non-chiral systems to test the validity of the approach.

Original languageAmerican English
Article number074106
JournalJournal of Chemical Physics
Volume143
Issue number7
DOIs
StatePublished - 21 Aug 2015
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2015 AIP Publishing LLC.

Fingerprint

Dive into the research topics of 'Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function'. Together they form a unique fingerprint.

Cite this